Polynitro diaza alkanes



United States POLYNITRO DIAZA ALKANES Milton B. Frankel, Pasadena, and Karl Klager, Monrovia, 'Calif., assignors to Aerojet-General Corporation, Azusa, Calif., a corporation of Ohio- No Drawing. Filed Mar. 7, 1951, Ser. No. 644,694 10 Claims. 01. 260-583) This invention relates to new compositions of matter and a method for their preparation. In'particulagthis invention relates to nitramines having the general formula:

wherein R is a nitro or alkyl radical and Aisan alkylene radical.

This application is a continuation-in-part of our copending United States patent application Serial No. 421, 986, filed April 8, 1954, now abandoned.

The nitro compounds of this invention are useful as high explosives and can be'used in any conventional explosive missile, projectiles, rocket, or the like, as the main explosive charge. An example of such a missile is disclosed in United States Patent No. 2,470,162, issued May 17, 1949. One way of using the high explosives of this invention in a device such as that disclosed in United States Patent No. 2,470,162, is to pack the crystalline explosive in powder form into the warhead of the missile. Alternatively, the crystals can be first pelletized and then packed. A charge thus prepared is sufliciently in-v sensitive to withstand the shock entailed in the ejection of a shell from a gun barrel or from a rocket launching tube under the pressure developed from ignition of a propellant charge, and can be caused to explode on operation of an impactor time fuse-mechanism firing a detonating explosive such as lead azide or mercury fulminate.

The compounds of this invention are readily prepared by reacting the corresponding amines with nitric acid, in accordance with the general reaction scheme set forth below:

wherein R and A are as defined above.

The amines useful as starting materials for this invention are readily prepared by condensing p-geminal polynitro alcohols with diamines, as disclosed in our copending application Serial No. 421,984, filed April 8, 1954.

To more fully illustrate this invention, the following examples are presented. It isto be understood, however, that these examples are presented merely as a means of illustration, and are not intended to limit the scope of the invention in any way.

EXAMPLE I Preparation of 1,1,I,3,6,6,9,11,11,I1-decanitr0-3,9-diaza undecane A solution of 250 ml. of 100% nitric acid and 250 ml. of acetic acid was cooled to 5 C. and 34 gm. of 1,1,1,6,

Patented Apr. 4, 1961 2 6,11,]1,11-octanitro-3,9-diaza undecane was added. The solution was then poured onto ice, causing -a white solid to precipitate. with water. Recrystallization from'hot 100% distilled ice nitric acid yielded a product having a M.P. of 170-175 C, with decomposition, and'exhibiting an-impact stability of -10-15 cm./2 kg. j The elemental analysis of the product is'as follows:

Calculated for C H N O Percent C, 17.77; percent H, 1.99; percent N, 27.64. Found: Percent C, 18.11; percent H, 2.00; percent N, 27.34. p

The heat of combustion was calculated to be 2044 caL/gm. and found to be 1978 cal/gm. The explosive values of the compound are as follows:

Lead block value 177 TNT=100.

Ballistic mortar value 155 TNT=100.

EXAMPLE II 2,2,7,7,12,12-hexanitro-4,10-diaza tridecane was reacted with nitric acid by following the procedure described in Example I. Recrystallization from acetone yielded a product having a M.P. of 206-208 C. The elemental analysis of the product is as follows:

Calculated for C H N O Percent C, 24.18; percent H, 3.32; percent N, 25.64. Found: Percent C, 24.76; percent H, 3.35; percent N, 24.98.. p

The heat of combustion was calculated to be 2878 cal/gm. and was found to be 2830 caL/grn. The explosive values of this compound are as follows:

Lead block value 128 TNT=100.

Ballistic mortar value TNT=100.

We have also found that amines such as 3,3,8,8,13,13- hexanitro-5,1l-diaza' pentadecane, 1,1,1,7,7,13,13,13-octanitro-3,11-diaza tridecane and 2,2,8,8,14,14-hexanitro-4, 12-diaza pentadecane are all readily nitrated with nitric acid to produce the corresponding nitramines, namely, 3,3,5,8,8,11,13,13-octanitro-5,ll-diaza pentadecane, 1, 1, 1,3,7,7,11,13,13,13-decanitro-3,1l-diaza tridecane and 2,2, 4,8,8,12,14,14-octanitro-4,12-diaza pentadecane.

It is apparent that any member ofthe disclosed series of nitramines can be prepared by merely selecting the appropriate amine and reacting it with nitric acid, in accordance with the teachings of this invention.

We claim:

1. As compositions of matter, nitramines having the general formula:

wherein R is a radical selected from the group'consisting of nitro and lower alkyl radicals and A is a lower alkylene radical.

2. As compositions of matter, nitramines having the general formula:

wherein A is a lower alkylene radical.

3. As compositions of matter, nitramines having the wherein R is a lower alkyl radical and A is a lower alkylene radical.

4. As a composition of matter, 1,1,1,3,6,6,9,11,11,11-

The product was collected and washeddecanitro-3,9-diaza undecane having the structural for- 5. As a composition of matter, 2,2,4,7,7,l0,12,l2-octanitro-4,10-diaza tridecane having the structural formula:

N01 N01 NO; N N0 OKs-( 3-GHQ-1 T-CH2CH2 CHzCHz%TCHr J-CH3 1 10, N 'oa I IOQ 6. The method of preparing nitramines having the gen which comprises reacting nitric acid with an amine having the general formula:

wherein R is a radical selected from a group consisting of lower alkyl and nitro radicals and A is a lower alkylene radical.

7. The method of preparing nitramines having the general formula:

NO; N0: N0, N02 No, No,-o-cHr-1 Ia-oHPh-om-A-iPom-h-No N02 1110: l l'oz which comprises reacting nitric acid with an amine having the general formula:

wherein A is a lower alkylene radical.

8. The method of preparing nitramines having the general formula:

which comprises reacting nitric acid with an amine having the general formula:

No references cited. 

1. AS COMPOSITIONS OF MATTER, NITRAMINES HAVING THE GENERAL FORMULA: 